Method and apparatus for electrowinning copper using ferrous/ferric anode reaction

ABSTRACT

The present invention relates, generally, to a method and apparatus for electrowinning metals, and more particularly to a method and apparatus for copper electrowinning using the ferrous/ferric anode reaction. In general, the use of a flow-through anode—coupled with an effective electrolyte circulation system—enables the efficient and cost-effective operation of a copper electrowinning system employing the ferrous/ferric anode reaction at a total cell voltage of less than about 1.5 V and at current densities of greater than about 26 Amps per square foot (about 280 A/m 2 ), and reduces acid mist generation. Furthermore, the use of such a system permits the use of low ferrous iron concentrations and optimized electrolyte flow rates as compared to prior art systems while producing high quality, commercially saleable product (i.e., LME Grade A copper cathode or equivalent), which is advantageous.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 12/126,552 filed May 23, 2008 and entitled “Method and Apparatus forElectrowinning Copper Using the Ferrous/Ferric Anode Reaction.” The '552application claims priority to U.S. application Ser. No. 10/629,497,filed Jul. 28, 2003 and entitled “Method And Apparatus forElectrowinning Copper Using the Ferrous/Ferric Anode Reaction.” Both the'552 application and the '497 application are incorporated by referenceherein in their entirety.

FIELD OF INVENTION

The present invention relates, generally, to a method and apparatus forelectrowinning metals, and more particularly to a method and apparatusfor copper electrowinning using the ferrous/ferric anode reaction.

BACKGROUND OF THE INVENTION

Efficiency and cost-effectiveness of copper electrowinning is and for along time has been important to the competitiveness of the domesticcopper industry. Past research and development efforts in this area havethus focused—at least in part—on mechanisms for decreasing the totalenergy requirement for copper electrowinning, which directly impacts thecost-effectiveness of the electrowinning process.

Conventional copper electrowinning, wherein copper is plated from animpure anode to a substantially pure cathode with an aqueouselectrolyte, occurs by the following reactions:

Cathode Reaction:

Cu²⁺+SO₄ ²⁻+2e ⁻→Cu₀+SO₄ ²⁻ (E⁰=+0.345 V)

Anode Reaction:

H₂O→½O₂+2H⁺+2e ⁻ (E⁰=−1.230 V)

Overall Cell Reaction:

Cu²⁺+SO₄ ²⁻+H₂O→Cu⁰+2H⁺+SO₄ ²⁻+½O₂ (E⁰=−0.855 V)

Conventional copper electrowinning according to the above reactions,however, exhibits several areas of potential improvement for, amongother things, improved economics, increased efficiency, and reduced acidmist generation. First, in conventional copper electrowinning, thedecomposition of water reaction at the anode produces oxygen (O₂) gas.When the liberated oxygen gas bubbles break the surface of theelectrolyte bath, they create an acid mist. Reduction or elimination ofacid mist is desirable. Second, the decomposition of water anodereaction used in conventional electrowinning contributes significantlyto the overall cell voltage via the anode reaction equilibrium potentialand the overpotential. The decomposition of water anode reactionexhibits a standard potential of 1.23 Volts (V), which contributessignificantly to the total voltage required for conventional copperelectrowinning. The typical overall cell voltage is approximately 2.0 V.A decrease in the anode reaction equilibrium potential and/oroverpotential would reduce cell voltage, and thus conserve energy anddecrease the total operating costs of the electrowinning operation.

One way that has been found to potentially reduce the energy requirementfor copper electrowinning is to use the ferrous/ferric anode reaction,which occurs by the following reactions:

Cathode Reaction:

Cu²⁺+SO₄ ²⁻+2e ⁻→Cu₀+SO₄ ²⁻ (E⁰=+0.345 V)

Anode Reaction:

2Fe²⁺→2Fe³⁺+2e ⁻ (E⁰=−0.770 V)

Overall Cell Reaction:

Cu²⁺+SO₄ ²⁻+2Fe²⁺→Cu⁰+2Fe³⁺+SO₄ ²⁻ (E⁰=−0.425 V)

The ferric iron generated at the anode as a result of this overall cellreaction can be reduced back to ferrous iron using sulfur dioxide, asfollows:

Solution Reaction:

2Fe³⁺+SO₂+2H₂O→2Fe²⁺+4H⁺+SO₄ ²⁻

The use of the ferrous/ferric anode reaction in copper electrowinningcells lowers the energy consumption of those cells as compared toconventional copper electrowinning cells that employ the decompositionof water anode reaction, since the oxidation of ferrous iron (Fe²⁺) toferric iron (Fe³⁺) occurs at a lower voltage than does the decompositionof water. However, maximum voltage reduction—and thus maximum energyreduction—cannot occur using the ferrous/ferric anode reaction unlesseffective transport of ferrous iron and ferric iron to and from,respectively, the cell anode(s) is achieved. This is because theoxidation of ferrous iron to ferric iron in a copper electrolyte is adiffusion-controlled reaction. This principle has been recognized andapplied by, among others, the U.S. Bureau of Mines Reno Research Centerand Sandoval et al. in U.S. Pat. No. 5,492,608, entitled “ElectrolyteCirculation Manifold for Copper Electrowinning Cells Which Use theFerrous/Ferric Anode Reaction.”

Although, in general, the use of the ferrous/ferric anode reaction inconnection with copper electrowinning is known, a number of deficienciesare apparent in the prior art regarding to the practical implementationof the ferrous/ferric anode reaction in copper electrowinning processes.For example, prior embodiments of the ferrous/ferric anode reaction incopper electrowinning operations generally have been characterized byoperating current density limitations, largely as a result of theinability to obtain a sufficiently high rate of diffusion of ferrousiron to the anode and ferric iron from the anode. Stated another way,because these prior applications have been unable to achieve optimumtransport of ferrous and ferric ions to and from the anode(s) in theelectrochemical cell, prior applications of the ferrous/ferric anodereaction have been unable to cost effectively produce copper cathode inelectrochemical cells employing largely conventional structuralfeatures.

SUMMARY OF THE INVENTION

The present invention relates to an improved copper electrowinningprocess and apparatus designed to address, among other things, theaforementioned deficiencies in prior art electrowinning systems. Theimproved process and apparatus disclosed herein achieves an advancementin the art by providing a copper electrowinning system that, byutilizing the ferrous/ferric anode reaction in combination with otheraspects of the invention, enables significant enhancement inelectrowinning efficiency, energy consumption, and reduction of acidmist generation as compared to conventional copper electrowinningprocesses and previous attempts to apply the ferrous/ferric anodereaction to copper electrowinning operations. As used herein, the term“alternative anode reaction” refers to the ferrous/ferric anodereaction, and the term “alternative anode reaction process” refers toany electrowinning process in which the ferrous/ferric anode reaction isemployed.

Enhancing the circulation of electrolyte in the electrowinning cellbetween the electrodes facilitates transport of copper ions to thecathode, increases the diffusion rate of ferrous iron to the anode, andfacilitates transport of ferric iron from the anode. Most significantly,as the diffusion rate of ferrous iron to the anode increases, theoverall cell voltage generally decreases, resulting in a decrease in thepower required for electrowinning the copper using an alternative anodereaction process.

While the way in which the present invention addresses thesedeficiencies and provides these advantages will be discussed in greaterdetail below, in general, the use of a flow-through anode—coupled withan effective electrolyte circulation system—enables the efficient andcost-effective operation of a copper electrowinning system employing theferrous/ferric anode reaction at a total cell voltage of less than about1.5 V and at current densities of greater than about 26 Amps per squarefoot (about 280 A/m²), and reduces acid mist generation. Furthermore,the use of such a system permits the use of low ferrous ironconcentrations and optimized electrolyte flow rates as compared to priorart systems while producing high quality, commercially saleable product(i.e., LME Grade A copper cathode or equivalent), which is advantageous.

In accordance with one aspect of an exemplary embodiment of theinvention, an electrochemical cell is configured such that copperelectrowinning may be achieved in an alternative anode reaction processwhile maintaining a current density of greater than about 26 A/ft² (280A/m²) of active cathode.

In accordance with another aspect of an exemplary embodiment of theinvention, an electrochemical cell is configured such that the cellvoltage is maintained at less than about 1.5 V during the operation ofan alternative anode reaction process.

In accordance with an aspect of yet another exemplary embodiment of theinvention, an alternative anode reaction process is operated such thatthe concentration of iron in the electrolyte is maintained at a level offrom about 10 to about 60 grams per liter.

In accordance with an aspect of yet another exemplary embodiment of theinvention, an alternative anode reaction process is operated such thatthe temperature is maintained at from about 110° F. (about 43° C.) toabout 180° F. (about 83° C.).

These and other features and advantages of the present invention willbecome apparent to those skilled in the art upon a reading of thefollowing detailed description when taken in conjunction with thedrawing figures, wherein there is shown and described variousillustrative embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

The subject matter of the present invention is particularly pointed outand distinctly claimed in the concluding portion of the specification. Amore complete understanding of the present invention, however, may bestbe obtained by referring to the detailed description and to the claimswhen considered in connection with the drawing figures, wherein likenumerals denote like elements and wherein:

FIG. 1 is a flow diagram for an electrowinning process in accordancewith one embodiment of the present invention;

FIG. 2 illustrates an electrochemical cell configured to operate inaccordance with one exemplary embodiment of the present invention; and

FIG. 3 illustrates an example of a flow-through anode with an example ofan in-anode electrolyte injection manifold in accordance with an aspectof another exemplary embodiment of the present invention.

FIG. 4 illustrates yet another example of a flow-through anode withanother example of an in-anode electrolyte injection manifold inaccordance with an aspect of another exemplary embodiment of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention exhibits significant advancements over prior artprocesses, particularly with regard to process efficiency, processeconomics, and reduction of acid mist generation. Moreover, existingcopper recovery processes that utilize conventional electrowinningprocess sequences may, in many instances, easily be retrofitted toexploit the many commercial benefits the present invention provides.

With initial reference to FIG. 1, an electrowinning process 100illustrating various aspects of an exemplary embodiment of the inventionis provided. Electrowinning process 100 generally comprises anelectrowinning stage 101, a ferrous iron regeneration stage 103, and anacid removal stage 105. Copper-rich commercial electrolyte 11 isintroduced to electrowinning stage 101 for recovery of the coppertherein. Electrowinning stage 101 produces cathode copper (stream notshown) and a ferric-rich electrolyte stream 13. At least a portion offerric-rich electrolyte stream 13 is introduced into ferrous ironregeneration stage 103 as electrolyte regeneration stream 15. Manifoldcirculation stream 16 comprises the portion of ferric-rich electrolytestream 13 not sent to ferrous iron regeneration stage 103, as well asrecycle streams 12 and 14 from ferrous iron regeneration stage 103 andacid removal stage 105, respectively, and serves as a flow control andfluid agitation mechanism in accordance with one aspect of the inventiondiscussed hereinbelow.

Generally speaking, increasing the operating current density in anelectrowinning cell increases the cell voltage. This increased voltagedemand translates into increased energy costs for producing copper,which affects the profitability of the electrowinning operation. On theother hand, certain other parameters in alternative anode reactionprocesses—such as, for example, temperature and iron concentration inthe electrolyte—may be controlled in a manner that mitigates the effectof increased current density on cell voltage. For instance, as thetemperature of the electrolyte is increased, cell voltage tends todecrease. Similarly, as the concentration of iron in the electrolyteincreases, voltage tends to decrease in electrowinning cells employingthe alternative anode reaction. Nevertheless, the mitigating effect ofincreased temperature and increased iron concentration on high cellvoltage is limited.

In general, processes and systems configured according to variousembodiments of the present invention enable the efficient andcost-effective utilization of the alternative anode reaction in copperelectrowinning at a cell voltage of less than about 1.5 V and at currentdensities of greater than about 26 A/ft² (about 280 A/m²). Furthermore,the use of such processes and/or systems reduces generation of acid mistand permits the use of low ferrous iron concentrations in theelectrolyte and optimized electrolyte flow rates, as compared to priorart systems, while producing high quality, commercially saleableproduct.

While various configurations and combinations of anodes and cathodes inthe electrochemical cell may be used effectively in connection withvarious embodiments of the invention, preferably a flow-through anode isused and electrolyte circulation is provided using an electrolyte flowmanifold capable of maintaining satisfactory flow and circulation ofelectrolyte within the electrowinning cell.

In accordance with other exemplary embodiments of the invention, asystem for operating an alternative anode reaction process includes anelectrochemical cell equipped with at least one flow-through anode andat least one cathode, wherein the cell is configured such that the flowand circulation of electrolyte within the cell enables the cell to beadvantageously operated at a cell voltage of less than about 1.5 V andat a current density of greater than about 26 A/ft². Various mechanismsmay be used in accordance with the present invention to enhanceelectrolyte flow, as detailed herein. For example, an electrolyte flowmanifold configured to inject electrolyte into the anode may be used, aswell as exposed “floor mat” type manifold configurations and otherforced-flow circulation means. In accordance with various embodiments ofthe invention, any flow mechanism that provides an electrolyte floweffective to transport ferrous iron to the anode, to transport ferriciron from the anode, and to transport copper ions to the cathode suchthat the electrowinning cell may be operated at a cell voltage of lessthan about 1.5 V and at a current density of greater than about 26A/ft², is suitable.

These and other exemplary aspects of the present invention are discussedin greater detail hereinbelow.

In accordance with one aspect of the invention, ferrous iron, forexample, in the form of ferrous sulfate (FeSO₄), is added to thecopper-rich electrolyte to be subjected to electrowinning, to cause theferrous/ferric (Fe²⁺/Fe³⁺) couple to become the anode reaction. In sodoing, the ferrous/ferric anode reaction replaces the decomposition ofwater anode reaction. As discussed above, because there is no oxygen gasproduced in the ferrous/ferric anode reaction, generation of “acid mist”as a result of the reactions in the electrochemical cell is eliminated.In addition, because the equilibrium potential of the Fe²⁺/Fe³⁺ couple(i.e., E⁰=−0.770 V) is less than that for the decomposition of water(i.e., E⁰=−1.230 V), the cell voltage is decreased, thereby decreasingcell energy consumption.

Moreover, as is discussed in greater detail hereinbelow, enhancedcirculation of electrolyte between the electrodes increases thediffusion rate of ferrous iron to the anode. As the diffusion rate offerrous iron to the anode increases, the overall cell voltage generallydecreases, resulting in a decrease in the power required forelectrowinning the copper.

In accordance with one exemplary embodiment of the present invention, aflow-through anode with an electrolyte injection manifold isincorporated into the cell as shown in FIG. 2. As used herein, the term“flow-through anode” refers to any anode configured to enableelectrolyte to pass through it. While fluid flow from the manifoldprovides electrolyte movement, a flow-through anode allows theelectrolyte in the electrochemical cell to flow through the anode duringthe electrowinning process. The use of a flow-through anode withmanifold electrolyte injection decreases cell voltage at lowerelectrolyte flow rates, as compared to the prior art, and at lowerelectrolyte iron concentrations as compared to the prior art, throughenhanced diffusion of ferrous iron to the anode. Prior art systems, forexample, relied upon a “brute force” approach to increasing currentdensity in electrowinning operations, elevating electrolyte flow rate,electrolyte temperature, and electrolyte iron concentration in theirattempts. Prior art attempts, however, achieved maximum currentdensities of only up to 26 A/ft², and even then, average cell voltageswere well above 1.0 V. Utilizing a flow-through anode in combinationwith effective electrolyte injection, however, the present inventors areable to operate electrowinning processes at current densities of 26A/ft² and cell voltages of well below 1.0 V, while also dramaticallydecreasing the electrolyte flow rate and electrolyte iron concentration.Decreasing iron concentration without adversely affecting the efficiencyor quality of the electrowinning operation is economically desirable,because doing so decreases iron make-up requirements and decreases theelectrolyte sulfate saturation temperature, and thus decreases the costof operating the electrowinning cell.

In accordance with various aspects of exemplary embodiments of theinvention, electrolyte injection manifolds with bottom injection, sideinjection, and/or in-anode injection are incorporated into the cell toenhance ferrous iron diffusion. EXAMPLE 1 herein demonstrates theeffectiveness of an in-anode electrolyte injection manifold fordecreasing cell voltage.

In accordance with an exemplary embodiment of the invention, an overallcell voltage of less than about 1.5 V is achieved, preferably less thanabout 1.20 V or about 1.25 V, and more preferably less than about 0.9 Vor about 1.0 V.

Generally speaking, as the operating current density in theelectrochemical cell increases, the copper plating rate increases.Stated another way, as the operating current density increases, morecathode copper is produced for a given time period and cathode activesurface area than when a lower operating current density is achieved.Alternatively, by increasing the operating current density, the sameamount of copper may be produced in a given time period, but with lessactive cathode surface area (i.e., fewer or smaller cathodes, whichcorresponds to lower capital equipment costs and lower operating costs).

As current density increases using the ferrous/ferric anode reaction,cell voltage tends to increase due in part to the depletion of ferrousions at the anode surface. This can be compensated for by increasingtransport of ferrous ions to the anode as current density increases inorder to maintain a low cell voltage. The prior art was limited tocurrent densities of 26 A/ft² (280 A/m²) and below for copperelectrowinning using the ferrous/ferric anode reaction in large partbecause of ferrous iron transport limitations. Stated another way,previous attempts that increased flow rates and increased ironconcentration in the electrolyte to achieve high current densities wereunsuccessful in decreasing overall cell voltage. Various embodiments ofthe present invention allow for operation at current densities above—andsignificantly above—26 A/ft² while maintaining cell voltages of lessthan about 1.5 V.

As will be described in greater detail hereinbelow, exemplaryembodiments of the present invention permit operation of electrochemicalcells using the ferrous/ferric anode reaction at current densities offrom about 26 to about 35 A/ft² at cell voltages of less than about 1.0V; up to about 40 A/ft² at cell voltages of less than about 1.25 V; andup to about 50 A/ft² or greater at cell voltages of less than about 1.5V.

In accordance with an exemplary embodiment of the invention, a currentdensity of from about 20 to about 50 amps per square foot of activecathode (about 215 A/m² to about 538 A/m²) is maintained, preferablygreater than about 26 A/ft² (280 A/m²), and more preferably greater thanabout 30 A/ft² (323 A/m²) of active cathode. It should be recognized,however, that the maximum operable current density achievable inaccordance with various embodiments of the present invention will dependupon the specific configuration of the process apparatus, and thus anoperating current density in excess of 50 A/ft² (538 A/m²) of activecathode may be achievable in accordance with the present invention.

One clear advantage of processes configured in accordance with variousembodiments of the present invention is that a higher current density ascompared to the prior art is achievable at the same cell voltage whenusing a flow-through anode with forced-flow manifold electrolyteinjection. For example, the U.S. Bureau of Mines, as reported in S. P.Sandoval, et al., “A Substituted Anode Reaction for ElectrowinningCopper,” Proceedings of Copper 95-COBRE 95 International Conference, v.III, pp. 423-435 (1995), achieved a current density of only about 258A/m² (about 24.0 A/ft²) in an experimental test wherein theelectrowinning cell was operated continuously for five days with twoconventional cathodes and three conventional anodes (i.e.,non-flow-through anodes) and with a side-injection circulation manifold.The electrolyte flow rate was about 0.24 gpm/ft² and the electrolytetemperature was approximately 104° F. The iron concentration in theelectrolyte measured approximately 28 g/L and the average cell voltageover the five-day test period was 0.94 V.

Results of experimental testing performed in accordance with anexemplary embodiment of the present invention, however, clearlydemonstrate the benefits of the present invention over the prior art. Insuch testing, a current density of about 30 A/ft²—twenty-five percentgreater than the current density achieved in the U.S. Bureau of Minestesting—was achieved using an electrowinning cell with threeconventional cathodes and four flow-through anodes (in this instance,titanium mesh anodes with an iridium oxide-based coating), and with abottom-injection “floor mat” circulation manifold. Electrolyte ironconcentration, electrolyte flow rate, temperature, and cell voltage weresimilar to those employed in the U.S. Bureau of Mines test.

Further illustrating the benefits of the present invention, EXAMPLE 1herein demonstrates that cell voltages of about 1.0 V and about 1.25 Vare achievable at current densities of about 35 A/ft² (377 A/m²) andabout 40 A/ft² (430 A/m²), respectively.

In conventional electrowinning processes utilizing the decomposition ofwater anode reaction, electrolyte mixing and electrolyte flow throughthe electrochemical cell are achieved by circulating the electrolytethrough the electrochemical cell and by the generation of oxygen bubblesat the anode, which cause agitation of the electrolyte solution as theoxygen bubbles rise to the surface of the electrolyte in the cell.However, because the ferrous/ferric anode reaction does not generateoxygen bubbles at the anode, electrolyte circulation is the primarysource of mixing in the electrochemical cell. The present inventors haveachieved an advancement in the art by recognizing that anelectrochemical cell configured to allow a significant increase in masstransport of relevant species between the anode (e.g., ferrous/ferricions) and the cathode (e.g., copper ions) by enhancing electrolyte flowand circulation characteristics when utilizing the alternative anodereaction would be advantageous.

Enhanced circulation of the electrolyte between the electrodes increasesthe rate of transport of ions to and from the electrode surfaces (forexample, copper ions to the cathode, ferrous ions to the anode, andferric ions away from the anode) and, as a result, generally decreasesthe overall cell voltage. Decreasing the cell voltage results in adecrease in the power demand for electrowinning. Enhancing circulationof the electrolyte, however, generally requires an increase in the powerdemand of the electrolyte pumping system. Thus, the objectives ofdecreasing cell voltage and increasing electrolyte circulation arepreferably balanced. In accordance with one aspect of an exemplaryembodiment of the invention, the total power requirement of theelectrochemical cell may be optimized by minimizing the sum of the powerrequired to circulate the electrolyte through the electrochemical celland the power used to electrowin the copper at the cathode.

Referring now to FIG. 2, an electrochemical cell 200 in accordance withvarious aspects of an exemplary embodiment of the invention is provided.Electrochemical cell 200 generally comprises a cell 21, at least oneanode 23, at least one cathode 25, and an electrolyte flow manifold 27comprising a plurality of injection holes 29 distributed throughout atleast a portion of the cell 21. In accordance with one aspect of anembodiment of the invention, electrochemical cell 200 comprises anexemplary apparatus for implementation of electrowinning step 101 ofelectrowinning process 100 illustrated in FIG. 1. These and otherexemplary aspects are discussed in greater detail hereinbelow.

In accordance with one aspect of an exemplary embodiment of the presentinvention, anode 23 is configured to enable the electrolyte to flowthrough it. As used herein, the term “flow-through anode” refers to ananode so configured, in accordance with one embodiment of the invention.

Any now known or hereafter devised flow-through anode may be utilized inaccordance with various aspects of the present invention. Possibleconfigurations include, but are not limited to, metal wool or fabric, anexpanded porous metal structure, metal mesh, multiple metal strips,multiple metal wires or rods, perforated metal sheets, and the like, orcombinations thereof. Moreover, suitable anode configurations are notlimited to planar configurations, but may include any suitablemultiplanar geometric configuration.

While not wishing to be bound by any particular theory of operation,anodes so configured allow better transport of ferrous iron to the anodesurface for oxidation, and better transport of ferric iron away from theanode surface. Accordingly, any configuration permitting such transportis within the scope of the present invention.

Anodes employed in conventional electrowinning operations typicallycomprise lead or a lead alloy, such as, for example, Pb—Sn—Ca. Onedisadvantage of such anodes is that, during the electrowinningoperation, small amounts of lead are released from the surface of theanode and ultimately cause the generation of undesirable sediments,“sludges,” particulates suspended in the electrolyte, or other corrosionproducts in the electrochemical cell and contamination of the coppercathode product. For example, copper cathode produced in operationsemploying a lead-containing anode typically comprises lead contaminantat a level of from about 1 ppm to about 4 ppm. Moreover, lead-containinganodes have a typical useful life limited to approximately four to sevenyears. In accordance with one aspect of a preferred embodiment of thepresent invention, the anode is substantially lead-free. Thus,generation of lead-containing sediments, “sludges,” particulatessuspended in the electrolyte, or other corrosion products and resultantcontamination of the copper cathode with lead from the anode is avoided.

Preferably, in accordance with an exemplary embodiment of the presentinvention, the anode is formed of one of the so-called “valve” metals,including titanium (Ti), tantalum (Ta), zirconium (Zr), or niobium (Nb).The anode may also be formed of other metals, such as nickel, or a metalalloy, intermetallic mixture, or a ceramic or cermet containing one ormore valve metals. For example, titanium may be alloyed with nickel(Ni), cobalt (Co), iron (Fe), manganese (Mn), or copper (Cu) to form asuitable anode. Preferably, the anode comprises titanium, because, amongother things, titanium is rugged and corrosion-resistant. Titaniumanodes, for example, when used in accordance with various aspects ofembodiments of the present invention, potentially have useful lives ofup to fifteen years or more.

The anode may also comprise any electrochemically active coating.Exemplary coatings include those provided from platinum, ruthenium,iridium, or other Group VIII metals, Group VIII metal oxides, orcompounds comprising Group VIII metals, and oxides and compounds oftitanium, molybdenum, tantalum, and/or mixtures and combinationsthereof. Ruthenium oxide and iridium oxide are preferred for use as theelectrochemically active coating on titanium anodes when such anodes areemployed in connection with various embodiments of the presentinvention. In accordance with one embodiment of the invention, the anodeis formed of a titanium metal mesh coated with an iridium-based oxidecoating. In another embodiment of the invention, the anode is formed ofa titanium mesh coated with a ruthenium-based oxide coating. Anodessuitable for use in accordance with various embodiments of the inventionare available from a variety of suppliers.

Conventional copper electrowinning operations use either a copperstarter sheet or a stainless steel or titanium “blank” as the cathode.In accordance with one aspect of an exemplary embodiment of theinvention, the cathode is configured as a metal sheet. The cathode maybe formed of copper, copper alloy, stainless steel, titanium, or anothermetal or combination of metals and/or other materials. As illustrated inFIG. 2 and as is generally well known in the art, the cathode 25 istypically suspended from the top of the electrochemical cell such that aportion of the cathode is immersed in the electrolyte within the celland a portion (generally a relatively small portion, less than abouttwenty percent (20%) of the total surface area of the cathode) remainsoutside the electrolyte bath. The total surface area of the portion ofthe cathode that is immersed in the electrolyte during operation of theelectrochemical cell is referred to herein, and generally in theliterature, as the “active” surface area of the cathode. This is theportion of the cathode onto which copper is plated duringelectrowinning.

In accordance with various embodiments of the present invention, thecathode may be configured in any manner now known or hereafter devisedby the skilled artisan.

In certain embodiments of the present invention, the effect of enhancedelectrolyte circulation on the cathode reaction is to promote effectivetransfer of copper ions. In order to promote a cathode deposit that isof high quality, the electrolyte circulation system should promoteeffective diffusion of copper ions to the cathode surface. When thecopper diffusion rate is sufficiently hindered, the crystal growthpattern can change to an unfavorable structure that may result in arough cathode surface. Excessive cathode roughness can cause an increasein porosity that can entrain electrolyte, and thus impurities, in thecathode surface. An effective diffusion rate of copper is one thatpromotes favorable crystal growth for smooth, high quality cathodes.Higher current density requires a higher rate of copper transfer to thecathode surface. For production of high quality, commercially acceptablecathodes, the maximum practical current density is limited in part bythe copper diffusion rate that promotes favorable crystal growthpatterns. In the present invention, the electrolyte circulation systemutilized in the electrochemical cell to facilitate the ionic transfer toor from the anode is also effective at promoting effective diffusion ofcopper ions to the cathode. For example, use of the flow through anodeenhances the copper ion transfer to the cathode in a similar manner tothe ferrous and ferric ion transfer to and from the anode.

In accordance with an exemplary embodiment of the present invention, thecopper concentration in the electrolyte for electrowinning isadvantageously maintained at a level of from about 20 to about 60 gramsof copper per liter of electrolyte. Preferably, the copper concentrationis maintained at a level of from about 30 to about 50 g/L, and morepreferably, from about 40 to about 45 g/L. However, various aspects ofthe present invention may be beneficially applied to processes employingcopper concentrations above and/or below these levels.

Generally speaking, any electrolyte pumping, circulation, or agitationsystem capable of maintaining satisfactory flow and circulation ofelectrolyte between the electrodes in an electrochemical cell such thatthe process specifications described herein are practicable may be usedin accordance with various embodiments of the invention.

Injection velocity of the electrolyte into the electrochemical cell maybe varied by changing the size and/or geometry of the holes throughwhich electrolyte enters the electrochemical cell. For example, withreference to FIG. 2 wherein electrolyte flow manifold 27 is configuredas tubing or piping inside cell 21 having injection holes 29, if thediameter of injection holes 29 is decreased, the injection velocity ofthe electrolyte is increased, resulting in, among other things,increased agitation of the electrolyte. Moreover, the angle of injectionof electrolyte into the electrochemical cell relative to the cell wallsand the electrodes may be configured in any way desired. Although anapproximately vertical electrolyte injection configuration isillustrated in FIG. 2 for purposes of reference, any number ofconfigurations of differently directed and spaced injection holes arepossible. For example, although the injection holes represented in FIG.2 are approximately parallel to one another and similarly directed,configurations comprising a plurality of opposing injection streams orintersecting injection streams may be beneficial in accordance withvarious embodiments of the invention.

In accordance with one embodiment of the invention, the electrolyte flowmanifold comprises tubing or piping suitably integrated with, attachedto, or inside the anode structure, such as, for example, insertedbetween the mesh sides of an exemplary flow-through anode. Such anembodiment is illustrated, for example, in FIG. 3, wherein manifold 31is configured to inject electrolyte between mesh sides 33 and 34 ofanode 32. Yet another exemplary embodiment is illustrated in FIG. 4,wherein manifold 41 is configured to inject electrolyte between meshsides 43 and 44 of anode 42. Manifold 41 includes a plurality ofinterconnected pipes or tubes 45 extending approximately parallel to themesh sides 43 and 44 of anode 42 and each having a number of holes 47formed therein for purposes of injecting electrolyte into anode 42,preferably in streams flowing approximately parallel to mesh sides 43and 44, as indicated in FIG. 4.

In accordance with another embodiment of the invention, the electrolyteflow manifold comprises an exposed “floor mat” type manifold, generallycomprising a group of parallel pipes situated length-wise along thebottom of the cell. Details of an exemplary manifold of suchconfiguration are disclosed in the Examples herein.

In accordance with yet another embodiment of the invention, the highflow rate and forced-flow electrolyte flow manifold is integrated intoor attached to opposite side walls and/or the bottom of theelectrochemical cell, such that, for example, the electrolyte injectionstreams are oppositely directed and parallel to the electrodes. Otherconfigurations are, of course, possible.

In accordance with various embodiments of the present invention, anyelectrolyte flow manifold configuration that provides an electrolyteflow effective to transport ferrous iron to the anode, to transportferric iron from the anode, and to transport copper ions to the cathodesuch that the electrowinning cell may be operated at a cell voltage ofless than about 1.5 V and at a current density of greater than about 26A/ft², is suitable.

In accordance with an exemplary embodiment of the invention, electrolyteflow rate is maintained at a level of from about 0.1 gallons per minuteper square foot of active cathode (about 4.0 L/min/m²) to about 1.0gallons per minute per square foot of active cathode (about 40.0L/min/m²). Preferably, electrolyte flow rate is maintained at a level offrom about 0.1 gallons per minute per square foot of active cathode(about 4.0 L/min/m²) to about 0.25 gallons per minute per square foot ofactive cathode (about 10.0 L/min/m²). It should be recognized, however,that the optimal operable electrolyte flow rate useful in accordancewith the present invention will depend upon the specific configurationof the process apparatus, and thus flow rates in excess of about 1.0gallons per minute per square foot of active cathode (in excess of about40.0 L/min/m²) or less than about 0.1 gallons per minute per square footof active cathode (less than about 4.0 L/min/m²) may be optimal inaccordance with various embodiments of the present invention.

Generally, as the operating temperature of the electrochemical cell(e.g., the electrolyte) increases, better plating at the cathode isachievable. While not wishing to be bound by any particular theory, itis believed that elevated electrolyte temperatures provide additionalreaction energy and may provide a thermodynamic reaction enhancementthat, at constant cell voltage, results in enhanced copper diffusion inthe electrolyte as temperature is increased. Moreover, increasedtemperature also may enhance ferrous diffusion, and can result inoverall reduction of the cell voltage, which in turn results in greatereconomic efficiency. EXAMPLE 2 demonstrates a decrease in cell voltagewith increasing electrolyte temperature. Conventional copperelectrowinning cells typically operate at temperature from about 115° F.to about 125° F. (from about 46° C. to about 52° C.).

In accordance with one aspect of an exemplary embodiment of the presentinvention, the electrochemical cell is operated at a temperature of fromabout 110° F. to about 180° F. (from about 43° C. to about 83° C.).Preferably, the electrochemical cell is operated at a temperature aboveabout 115° F. (about 46° C.) or about 120° F. (about 48° C.), andpreferably at a temperature below about 140° F. (about 60° C.) or about150° F. (about 65° C.). However, in certain applications, temperaturesin the range of about 155° F. (about 68° C.) to about 165° F. (about 74°C.) may be advantageous.

It should be recognized, however, that while higher operatingtemperatures may be beneficial for the reasons outlined above, operationat such higher temperatures may require the use of materials ofconstruction designed and selected to satisfactorily withstand the morerigorous operating conditions. In addition, operation at highertemperatures may require increased energy demands.

The operating temperature of the electrochemical cell may be controlledthrough any one or more of a variety of means well known in the art,including, for example, an immersion heating element, an in-line heatingdevice (e.g., a heat exchanger), or the like, preferably coupled withone or more feedback temperature control means for efficient processcontrol.

A smooth plating surface is optimal for cathode quality and purity,because a smooth cathode surface is more dense and has fewer cavities inwhich electrolyte can become entrained, thus introducing impurities tothe surface. Although it is preferable that the current density andelectrolyte flow rate parameters be controlled such that a smoothcathode plating surface is achievable, operating the electrochemicalcell at a high current density may nonetheless tend to result in a roughcathode surface. Thus, in accordance with one aspect of an exemplaryembodiment of the present invention, an effective amount of a platingreagent is added to the electrolyte stream to enhance the platingcharacteristics—and thus the surface characteristics—of the cathode,resulting in improved cathode purity. Any plating reagent effective inimproving the plating surface characteristics, namely, smoothness andporosity, of the cathode may be used. For example, suitable platingreagents (sometimes called “smoothing agents”) may include thiourea,guar gums, modified starches, polyacrylic acid, polyacrylate, chlorideion, and/or combinations thereof may be effective for this purpose. Whenused, an effective concentration of the plating reagent in theelectrolyte—or, stated another way, the effective amount of platingreagent required—invariably will depend upon the nature of theparticular plating reagent employed; however, the plating reagentconcentration generally will be in the range of from about 20 grams ofplating reagent per tonne of copper plated to about 1000 g/tonne.

As ferrous iron is oxidized at the anode in the electrochemical cell,the concentration of ferrous iron in the electrolyte is naturallydepleted, while the concentration of ferric iron in the electrolyte isnaturally increased. In accordance with one aspect of an exemplaryembodiment of the invention, the concentration of ferrous iron in theelectrolyte is controlled by addition of ferrous sulfate to theelectrolyte. In accordance with another embodiment of the invention, theconcentration of ferrous iron in the electrolyte is controlled bysolution extraction (SX) of iron from copper leaching solutions.

In order for the ferrous/ferric couple to maintain a continuous anodereaction, the ferric iron generated at the anode preferably is reducedback to ferrous iron to maintain a satisfactory ferrous concentration inthe electrolyte. Additionally, the ferric iron concentration preferablyis controlled to achieve satisfactory current efficiency in theelectrochemical cell.

In accordance with an exemplary embodiment of the present invention, thetotal iron concentration in the electrolyte is maintained at a level offrom about 10 to about 60 grams of iron per liter of electrolyte.Preferably, the total iron concentration in the electrolyte ismaintained at a level of from about 20 g/L to about 40 g/L, and morepreferably, from about 25 g/L to about 35 g/L. It is noted, however,that the total iron concentration in the electrolyte may vary inaccordance with various embodiments of the invention, as total ironconcentration is a function of iron solubility in the electrolyte. Ironsolubility in the electrolyte varies with other process parameters, suchas, for example, acid concentration, copper concentration, andtemperature. As explained hereinabove, decreasing iron concentration inthe electrolyte is generally economically desirable, because doing sodecreases iron make-up requirements and decreases the electrolytesulfate saturation temperature, and thus decreases the cost of operatingthe electrowinning cell.

In accordance with an exemplary embodiment of the present invention, theferric iron concentration in the electrolyte is maintained at a level offrom about 0.001 to about 10 grams of ferric iron per liter ofelectrolyte. Preferably, the ferric iron concentration in theelectrolyte is maintained at a level of from about 1 g/L to about 6 g/L,and more preferably, from about 2 g/L to about 4 g/L.

Referring again to FIG. 1, in accordance with another aspect of anexemplary embodiment of the invention, the concentration of ferric ironin the electrolyte within the electrochemical cell is controlled byremoving at least a portion of the electrolyte from the electrochemicalcell, for example, as illustrated in FIG. 1 as electrolyte regenerationstream 15 of process 100.

In accordance with one aspect of an exemplary embodiment of theinvention, sulfur dioxide 17 may be used to reduce the ferric iron inelectrolyte regeneration stream 15. Although reduction of Fe³⁺ to Fe²⁺in electrolyte regeneration stream 15 in ferrous regeneration stage 103may be accomplished using any suitable reducing reagent or method,sulfur dioxide is particularly attractive as a reducing agent for Fe³⁺because it is generally available from other copper processingoperations, and because sulfuric acid is generated as a byproduct. Uponreacting with ferric iron in a copper-containing electrolyte, the sulfurdioxide is oxidized, forming sulfuric acid. The reaction of sulfurdioxide with ferric iron produces two moles of sulfuric acid for eachmole of copper produced in the electrochemical cell, which is one molemore of acid than is typically required to maintain the acid balancewithin the overall copper extraction process, when solution extraction(SX) is used in conjunction with electrowinning. The excess sulfuricacid may be extracted from the acid-rich electrolyte (illustrated inFIG. 1 as stream 18) generated in the ferrous regeneration stage for usein other operations, such as, for example, leaching operations.

With reference to FIG. 1, the acid-rich electrolyte stream 18 fromferrous regeneration stage 103 may be returned to electrowinning stage101 via electrolyte recycle streams 12 and 16, may be introduced to acidremoval stage 105 for further processing, or may be split (as shown inFIG. 1) such that a portion of acid-rich electrolyte stream 18 returnsto electrowinning stage 101 and a portion continues to acid removalstage 105. In acid removal stage 105, excess sulfuric acid is extractedfrom the acid-rich electrolyte and leaves the process via acid stream19, to be neutralized or, preferably, used in other operations, such as,for example a heap leach operation. The acid-reduced electrolyte stream14 may then be returned to electrowinning stage 101 via electrolyterecycle stream 16, as shown in FIG. 1.

In sum, copper electrowinning using the ferrous/ferric anode reaction inaccordance with one embodiment of the present invention produces twoproducts—cathode copper and sulfuric acid.

In accordance with another aspect of an exemplary embodiment of theinvention, the ferric-rich electrolyte is contacted with sulfur dioxidein the presence of a catalyst, such as, for example, activated carbonmanufactured from bituminous coal, or other types of carbon with asuitable active surface and suitable structure. The reaction of sulfurdioxide and ferric iron is preferably monitored such that theconcentration of ferric iron and ferrous iron in the acid-richelectrolyte stream produced in the ferrous regeneration stage can becontrolled. In accordance with an aspect of another embodiment of theinvention, two or more oxidation-reduction potential (ORP) sensors areused—at least one ORP sensor in the ferric-rich electrolyte lineupstream from the injection point of sulfur dioxide, and at least oneORP sensor downstream from the catalytic reaction point in theferric-lean electrolyte. The ORP measurements provide an indication ofthe ferric/ferrous ratio in the solution; however, the exactmeasurements depend on overall solution conditions that may be unique toany particular application. Those skilled in the art will recognize thatany number of methods and/or apparatus may be utilized to monitor andcontrol the ferric/ferrous ratio in the solution. The ferric-richelectrolyte will contain from about 0.001 to about 10 grams per literferric iron, and the ferric-lean electrolyte will contain up to about 6grams per liter ferric iron.

The following examples illustrate, but do not limit, the presentinvention.

Example 1

TABLE 1 demonstrates the advantages of a flow-through anode within-anode electrolyte injection for achieving low cell voltage. Anin-anode manifold produces a lower cell voltage at the same flow ordecreases flow requirements at the same current density versus bottominjection. TABLE 1 also demonstrates that a cell voltage below 1.10 V isachievable at a current density of about 35 A/ft² (377 A/m²) and a cellvoltage below 1.25 V is achievable at a current density of about 40A/ft² (430 A/m²).

Test runs A-F were performed using an electrowinning cell of generallystandard design, comprising three full-size conventional cathodes andfour full-size flow-through anodes. The cathodes were constructed of 316stainless steel and each had an active depth of 41.5 inches and anactive width of 37.5 inches (total active surface area of 21.6 ft² percathode). Each anode had an active width of 35.5 inches and an activedepth of 39.5 inches and was constructed of titanium mesh with aniridium oxide-based coating. The anodes used in accordance with thisEXAMPLE 1 were obtained from Republic Anode Fabricators of Strongsville,Ohio, USA.

Test duration was five days (except test runs C, D, E and F, which were60-minute tests designed to measure voltage only, at constantconditions), with continuous 24-hour operation of the electrowinningcell at approximately constant conditions. Voltage measurements weretaken once per day using a handheld voltage meter and voltages weremeasured bus-to-bus. The stated values for average cell voltage in TABLE1 represent the average voltage values over the six-day test period.Electrolyte flow measurements were performed by a continuous electronicflow meter (Magmeter), and all electrolyte flow rates in TABLE 1 areshown as gallons per minute of electrolyte per square foot of cathodeplating area. The plating reagent utilized in all test runs was PD 4201modified starch, obtained from Chemstar from Minneapolis, Minn. Theconcentration of plating reagent in the electrolyte was maintained inthe range of 250-450 grams per plated ton of copper.

Electrolyte temperature was controlled using an automatic electricheater (Chromalox). Iron addition to the electrolyte was performed usingferrous sulfate crystals (18% iron). Copper and iron concentrationassays were performed using standard atomic absorption tests. Copperconcentration in the electrolyte was maintained at a level of about41-46 g/L using solution extraction.

The concentration of sulfuric acid in the electrolyte was maintained ata level of about 150-160 g/L using an Eco-Tec sulfuric acid extractionunit (acid retardation process).

The current to each electrowinning cell was set using a standardrectifier. The operating current density for each test run wascalculated by dividing the total Amps on the rectifier setting by thetotal cathode plating area (i.e., 64.8 ft²).

Ferrous regeneration was accomplished using sulfur dioxide gas, whichwas injected into an electrolyte recycle stream, then passed through anactivated carbon bed in order to catalyze the ferric reduction reaction.The reaction was controlled using ORP sensors, which measured ORP in therange of 390 to 410 mV (versus standard silver chloride referencejunction). Sufficient sulfur dioxide was injected into the electrolyterecycle stream such that the ORP was maintained within the range of 390to 410 mV.

Average copper production rate for test runs A and B, which wereoperated at a current density of 30 A/ft², was 112 lbs. per day. Thecopper cathode produced for test runs A and B measured less than 0.3 ppmlead and less than 5 ppm sulfur. Copper purity did not vary overallaccording to the specific test conditions employed. Copper assays ontest runs C—F were not performed because of the relatively short testduration.

Test runs A, C, and E were performed using a bottom-injection “floormat” injection manifold configuration. The bottom-injection manifoldincluded eleven 1″ diameter PVC pipes configured to run the length ofthe electrowinning cell (i.e., approximately perpendicular to the activesurfaces of the electrodes). Each of the eleven pipes positioned one3/16″ diameter hole in each electrode gap (i.e., there were eleven holesapproximately evenly spaced within each electrode gap).

Test runs A, D, and F were performed using an in-anode injectionmanifold configuration. The in-anode injection manifold was configuredusing a distribution supply line adjacent to the electrodes, with directelectrolyte supply lines comprising ⅜″ ID×¼″ OD or ¼″ ID×⅜″ ODpolypropylene tubing branching from the distribution supply line andleading to each anode. Each electrolyte supply line included fiveequally-spaced dropper tubes that branched from the electrolyte supplyline and were positioned to inject electrolyte directly into the anode,between the mesh surfaces of the anode. No electrolyte injectionoccurred directly adjacent to the cathodes.

TABLE 1 Electrolyte Cathode Current Manifold Electrolyte ElectrolyteElectrolyte Average Cell Density, Distributor Iron Conc., Flow,Temperature, Voltage, Test A/ft² Design g/L gpm/ft² ° F. V A 30 Bottom25.5 0.41 125 0.95 Injection B 30 In-Anode 25.5 0.41 125 0.90 InjectionC 35 Bottom 28 0.66 125 1.02 Injection D 35 In-Anode 28 0.24 125 1.10Injection E 40 Bottom 28 0.66 125 1.12 Injection F 40 In-Anode 28 0.24125 1.25 Injection

Example 2

TABLE 2 demonstrates that increasing temperature decreases cell voltage.

Test runs A-C were performed using an electrowinning cell of generallystandard design, comprising three full-size conventional cathodes andfour full-size flow-through anodes. The cathodes were constructed of 316stainless steel and each had an active depth of 41.5 inches and anactive width of 37.5 inches (total active surface area of 21.6 ft² percathode). Each anode had an active width of 35.5 inches and an activedepth of 39.5 inches and was constructed of titanium mesh with aniridium oxide-based coating. The anodes used in accordance with thisEXAMPLE 2 were obtained from Republic Anode Fabricators of Strongsville,Ohio, USA.

Test duration was six days, with continuous 24-hour operation of theelectrowinning cell at approximately constant conditions. Voltagemeasurements were taken once per day using a handheld voltage meter andvoltages were measured bus-to-bus. The stated values for average cellvoltage in TABLE 2 represent the average voltage values over the six-daytest period. Electrolyte flow measurements were performed by acontinuous electronic flow meter (Magmeter), and all electrolyte flowrates in TABLE 2 are shown as gallons per minute of electrolyte persquare foot of cathode plating area. The plating reagent utilized in alltest runs was PD 4201 modified starch, obtained from Chemstar fromMinneapolis, Minn. The concentration of plating reagent in theelectrolyte was maintained in the range of 250-450 grams per plated tonof copper.

Electrolyte temperature was controlled using an automatic electricheater (Chromalox). Iron addition to the electrolyte was performed usingferrous sulfate crystals (18% iron). Copper and iron concentrationassays were performed using standard atomic absorption tests. Copperconcentration in the electrolyte was maintained at a level of about41-46 g/L using solution extraction.

The concentration of sulfuric acid in the electrolyte was maintained ata level of about 150-160 g/L using an Eco-Tec sulfuric acid extractionunit (acid retardation process).

The current to each electrowinning cell was set using a standardrectifier. The operating current density for each test run wascalculated by dividing the total Amps on the rectifier setting by thetotal cathode plating area (i.e., 64.8 ft²).

Ferrous regeneration was accomplished using sulfur dioxide gas, whichwas injected into an electrolyte recycle stream, then passed through anactivated carbon bed in order to catalyze the ferric reduction reaction.The reaction was controlled using ORP sensors, which measured ORP in therange of 390 to 410 mV (versus standard silver chloride referencejunction). Sufficient sulfur dioxide was injected into the electrolyterecycle stream such that the ORP was maintained within the range of 390to 410 mV.

Average copper production rate for all test runs, which were operated ata current density of 30 A/ft², was 112 lbs. per day. The copper cathodeproduced for all test runs generally measured less than 0.3 ppm lead andless than 5 ppm sulfur. Copper purity did not vary overall according tothe specific test conditions employed.

Test runs were performed using a bottom-injection “floor mat” injectionmanifold configuration. The bottom-injection manifold included eleven 1″diameter PVC pipes configured to run the length of the electrowinningcell (i.e., approximately perpendicular to the active surfaces of theelectrodes). Each of the eleven pipes positioned one 3/16″ diameter holein each electrode gap (i.e., there were eleven holes approximatelyevenly spaced within each electrode gap).

TABLE 2 Electrolyte Cathode Current Manifold Electrolyte ElectrolyteElectrolyte Average Cell Density, Distributor Iron Conc. Flow,Temperature, Voltage, Test A/ft² Design g/L gpm/ft² ° F. V A 30 Bottom28.6 0.28 125 0.92 Injection B 30 Bottom 27.2 0.28 135 0.88 Injection C30 Bottom 26.9 0.28 125 0.95 Injection

An effective and efficient method of copper electrowinning using theferrous/ferric-sulfur dioxide anode reaction has been presented herein.Further, the present inventors have advanced the art of copperhydrometallurgy by recognizing the advantages of using theferrous/ferric anode reaction in connection with copper electrowinningprocesses, and have developed an improved system for utilizing theferrous/ferric anode reaction to achieve greater efficiency overconventional copper electrowinning processes.

The present invention has been described above with reference to anumber of exemplary embodiments and examples. It should be appreciatedthat the particular embodiments shown and described herein areillustrative of the invention and its best mode and are not intended tolimit in any way the scope of the invention as set forth in the claims.Those skilled in the art having read this disclosure will recognize thatchanges and modifications may be made to the exemplary embodimentswithout departing from the scope of the present invention. These andother changes or modifications are intended to be included within thescope of the present invention, as expressed in the following claims.

1. A method of electrowinning copper comprising: introducing acopper-containing electrolyte into an electrolytic cell comprising atleast one flow-through anode, at least one plate cathode, a floor, and aceiling; and flowing said copper-containing electrolyte through aplurality of injection holes located on at least one of said floor andsaid ceiling, wherein said copper-containing electrolyte comprisessolubilized ferrous iron.
 2. The method according to claim 1, furthercomprising flowing said copper-containing electrolyte through anelectrolyte flow manifold.
 3. The method according to claim 1, furthercomprising operating said electrolytic cell at a predetermined cellvoltage and at a predetermined current density, wherein said cellvoltage is less than about 1.5 Volts and wherein said current density isgreater than about 26 amperes per square foot of active plate cathode.4. The method according to claim 1, further comprising maintaining thetemperature of said copper-containing electrolyte in the range of fromabout 110° F. to about 180° F.
 5. A method of electrowinning coppercomprising: introducing a copper-containing electrolyte streamcomprising copper and ferrous iron into an electrolytic cell comprisinga flow-through anode and a cathode; flowing said copper-containingelectrolyte through an electrolyte flow manifold; oxidizing at least aportion of said ferrous iron in said copper-containing electrolyte atsaid flow-through anode from ferrous iron to ferric iron; and removingat least a portion of said copper from said copper-containingelectrolyte at said cathode.
 6. The method according to claim 5, furthercomprising operating said electrolytic cell at a cell voltage, whereinsaid cell voltage is less than about 1.5 Volts.
 7. The method accordingto claim 6, further comprising operating said electrolytic cell at acurrent density, wherein said current density is greater than about 26amperes per square foot of active cathode.
 8. The method according toclaim 5, further comprising: removing at least a portion of said ferriciron from said electrolytic cell in an electrolyte regeneration stream;reducing at least a portion of said ferric iron in said electrolyteregeneration stream to ferrous iron to form a regenerated electrolytestream; and returning at least a portion of said regenerated electrolytestream to said electrolytic cell.